Modeling of water transport through the membrane electrode assembly for direct methanol fuel cells

In this work, a one-dimensional, isothermal two-phase mass transport model is developed to investigate the water transport through the membrane electrode assembly (MEA) for liquid-feed direct methanol fuel cells (DMFCs). The liquid (methanol–water solution) and gas (carbon dioxide gas, methanol vapor and water vapor) two-phase mass transport in the porous anode and cathode is formulated based on classical multiphase flow theory in porous media. In the anode and cathode catalyst layers, the simultaneous three-phase (liquid and vapor in pores as well as dissolved phase in the electrolyte) water transport is considered and the phase exchange of water is modeled with finite-rate interfacial exchanges between different phases. This model enables quantification of the water flux corresponding to each of the three water transport mechanisms through the membrane for DMFCs, such as diffusion, electro-osmotic drag, and convection. Hence, with this model, the effects of MEA design parameters on water crossover and cell performance under various operating conditions can be numerically investigated.     

Enhancement of water retention in the membrane electrode assembly for direct methanol fuel cells operating with neat methanol

It is desirable to operate a direct methanol fuel cell (DMFC) with neat methanol to maximize the specific energy of the DMFC system, and hence increasing its runtime. A way to achieve the neat-methanol operation is to passively transport the water produced at the cathode through the membrane to the anode to facilitate the methanol oxidation reaction (MOR). To achieve a performance of the MOR similar to that under the conventional diluted methanol operation, both the water transport rate and the local water concentration in the anode catalyst layer (CL) are required to be sufficiently high. In this work, a thin layer consisting of nanosized SiO₂ particles and Nafion ionomer (referred to as a water retention layer hereafter) is coated onto each side of the membrane. Taking advantage of the hygroscopic nature of SiO₂, the cathode water retention layer can help maintain the water produced from the cathode at a higher concentration level to enhance the water transport to the anode, while the anode retention layer can retain the water that is transported from the cathode. As a result, a higher water transport rate and a higher water concentration at the anode CL can be achieved. The formed membrane electrode assembly (MEA) with the added water retention layers is tested in a passive DMFC and the results show that this MEA design yields a much higher power density than the MEA without water retention layers does.     

Multi-dimensional liquid water transport in the cathode of a PEM fuel cell with consideration of the micro-porous layer (MPL)

A multi-dimensional two-phase PEM fuel cell model, which is capable of handling the liquid water transport across different porous materials, including the catalyst layer (CL), the micro-porous layer (MPL), and the macro-porous gas diffusion medium (GDM), has been developed and applied in this paper for studying the liquid water transport phenomena with consideration of the MPL. Numerical simulations show that the liquid water saturation would maintain the highest value inside the catalyst layer while it possesses the lowest value inside the MPL, a trend consistent qualitatively with the high-resolution neutron imaging data. The present multi-dimensional model can clearly distinguish the different effects of the current-collecting land and the gas channel on the liquid water transport and distribution inside a PEM fuel cell, a feature lacking in the existing one-dimensional models. Numerical results indicate that the MPL would serve as a barrier for the liquid water transport on the cathode side of a PEM fuel cell.     

Laser perforated fuel cell diffusion media. Part I: Related changes in performance and water content

In this study, cathode-side, bi-layered diffusion media (DM) samples with micro-porous layer were perforated with 300 μm laser-cut holes (covering 15% of the surface area in a homogenous pattern) using a ytterbium fiber laser to investigate the effect of structural changes on the gas and water transport. Under reduced humidity conditions (50% inlet relative humidity on the anode and cathode), the perforated DM were observed to increase the potential by an average of 6% for current densities ranging from 0.2 to 1.4 A cm⁻². However, the perforated DM showed reduced performance for current densities greater than 1.4 A cm⁻² and at all currents under high-humidity conditions. Neutron radiography experiments were also performed to understand the changes in liquid water retention characteristics of DM due to the laser perforations. Significant water accumulation and water redistribution were observed in the perforated DM, which helps explain the observed performance behavior. The results indicate that the perforations act as water pooling and possible channeling locations, which significantly alter the water condensation, storage, and transport scheme within the fuel cell. These observations suggest that proper tailoring of fuel cell DM possesses significant potential to enable fuel cell operations with reduce liquid overhead and high performance.     

On the influence of the anodic porous transport layer on PEM electrolysis performance at high current densities

In this study, the influence of the anodic porous transport layer (PTL) on the performance of a proton exchange membrane (PEM) electrolysis laboratory test cell was investigated up to a current density of 5 A*cm⁻². Operation parameters such as water volume flow rate (0.2–0.8 l*min⁻¹), temperature (40–80 °C) and pressure (1–30 barg) have been varied to study their influence on the polarisation curve. Special attention has been paid to the appearance of mass transport losses (MTL) and their dependency on the operation parameters. Two stack designs that are commercially in use - one with and one without flow channels underneath the PTL - were tested and evaluated. Fundamental differences in performance have been observed between the two cell designs. Operation parameters only show impact on performance for the configuration without flow channels. Here, MTL were observed in several cases already for current densities around and above 1.0 A*cm⁻². An increase in pressure, temperature or water flow rate reduces MTL for these configurations.     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

Effect of operating conditions on water management of membrane electrode assembly for direct methanol fuel cell

介绍了直接甲醇燃料电池(DMFCs)膜电极的水平衡研究对单电池性能和稳定性的影响,研究了电池操作温度,空气流量及电流密度等操作条件对膜电极水平衡的影响.通过调节操作条件改变净水传输系数,进一步表征膜电极水平衡对电池稳定性的影响.结果表明,单电池在60 ℃,阴极常压空气80 mL/min进料,100 mA/cm²条件下工作具有较好的水平衡,最后,测试了单电池在该条件下的稳定性,测试结果表明电池稳定运行200 h后,性能没有明显衰减.     

The effect of operating parameters on water transport in PEM fuel cells

Water content in the membrane and the presence of liquid water in the catalyst layers (CL) and the gas diffusion layers (GDL) play a very important role in the performance of a PEM fuel cell. To study water transport in a PEM fuel cell, a two‐phase flow mathematical model is developed. This model couples the continuity equation, momentum conservative equation, species conservative equation, and water transport equation in the membrane. The modeling results of fuel cell performances agree well with measured experimental results. Then this model is used to simulate water transport and current density distribution in the cathode of a PEM fuel cell. The effects of operating pressure, cell temperature, and humidification temperatures on the net water transfer through the membrane, liquid water saturation, and current density distribution are studied. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 35(2): 89–100, 2006; Published online in Wiley InterScience ( www.interscience. wiley.com ). DOI 10.1002/htj.20107     

Increasing the performance of gas diffusion layer by insertion of small hydrophilic layer in proton-exchange membrane fuel cells

The present study applied Lattice Boltzmann method (LBM) for examining the transport of liquid water in a GDL carbonic paper of polymer electrolyte membrane (PEM) fuel cells. The stochastic method is used for GDL carbonic paper reconstruction. In order to study the behavior of liquid water, different simulations are carried out on the reconstructed GDL. While removing from the GDL of a PEM fuel cell, the dynamics of liquid water is simulated by LBM in this study. The effects that the wettability of GDL imposes on the removal process and liquid water distribution are investigated. In addition, the dynamic behaviors and the saturation process of the liquid water in GDL in a steady state and a transient mode are also explored. The effects of surface wettability on the effective clusters in GDL, merging of different clusters and the loops developed by the fingers are investigated. Moreover, the effects of mixed wettability on the liquid water dynamic behavior and liquid water saturation within the GDL are studied in detail. The results show that the best location for insertion of the hydrophilic layer inside the GDL is near the GDL-GC interface. In this case, the time required for liquid water to reach the GDL/GC interface is reduced about 17% than purely hydrophobic GDL. A decrease of 18.7% in the steady-state saturation level is also observed by insertion of hydrophilic layer; therefore, use of hydrophilic layer near GDL-GC interface is more effective than increasing the contact angle of GDL-fibers. Different validation studies are also reported to show the accuracy of the model.     

Fluid visualization and heat-transfer tests in a 180-deg round turned channel with a perforated divider

This study provided a new configuration of the 180-deg round turned channel with a perforated divider, as well as experimentally investigated the effect of perforations on the fluid flow and heat transfer. The flow visualizations and heat-transfer tests indicated that the big diameter of perforation and the positive angle of perforation changed the fluid flow pattern and the local Nusselt-number distribution strongly by comparing those of non-perforation system. The big-diameter perforations decreased the average Nusselt number, especially at the positive angle of perforations; while the number and location of perforations did not result in obvious influence herein. Besides, the average Nusselt number for the system of small perforations was about 3–8% higher than that of non-perforation one. Therefore, this work demonstrated that by adjusting the size and angle of perforations, this new cooling channel could achieve spatial thermal regulation or enhance the total heat transfer.     

Electrochemical impedance investigation of proton exchange membrane fuel cells experienced subzero temperature

Polarization losses of the fuel cells with different residual water amount frozen at subzero temperature were investigated by electrochemical impedance spectroscopy (EIS) taking into account the ohmic resistance, charge transfer process, and oxygen mass transport. The potential-dependent impedance before and after eight freeze/thaw cycles suggested that the ohmic resistance did not change, while the change of the charge transfer resistance greatly depended on the residual water amount. Among the four cells, the mass transport resistance of the cell with the largest water amount increased significantly even at the small current density region. According to the thin film-flooded agglomerate model, the interfacial charge transfer process and oxygen mass transport within the agglomerate and through the ionomer thin film in the catalyst layer both contributed to the high frequency impedance arc. From the analysis of the Tafel slopes, the mechanism of the oxygen reduction reaction (ORR) was the same after the cells experienced subzero temperature. The agglomerate diffusion changed a little in all cells and the thin film diffusion effect was obvious for the cell with the largest residual water amount. These results indicated that the slower oxygen diffusion within the catalyst layer (CL) was the main contributor for the evident performance loss after eight freeze/thaw cycles.     

Lattice Boltzmann method modeling and experimental study on liquid water characteristics in the gas diffusion layer of proton exchange membrane fuel cells

Water transport through the gas diffusion layer (GDL) is vital to proton exchange membrane fuel cells (PEMFCs), especially under flooding conditions. In this paper, a two-dimensional (2D) lattice Boltzmann method (LBM) is applied to reveal the water dynamic characteristics in GDL, and the computational domain is reconstructed based on the experiment. In-situ experiments, including I–V performance and electrochemical impedance spectroscopy (EIS) tests under flooding conditions, are carried out and analyzed. It is found that the porosity distribution inside the GDL is a crucial factor in water dynamic behavior research. The horizontal liquid water saturation (HS_w) under the channel of real GDL (with porosity distribution) at 0.4 relative thickness are 3.2 times, 2.1 times and 3.4 times higher than the ideal GDL (without porosity distribution) in the case of 0.8 mm, 1.2 mm and 2.0 mm, respectively. The numerical simulation and experimental study show that water dynamic characteristics under the rib influence cell performance directly. In our LBM model, the GDL water distribution inconsistency (Var_w) under 2.0 mm width rib is 43.1% and 28.0% higher than that under the 0.8 mm and 1.2 mm rib, respectively. With the rib wider from 0.8 mm to 2.0 mm, some parts of cell impedance such as R_mt, R_ct, and L_mt increase 64.22%, 98.89%, and 47.46%, respectively. However, GDL under the channel shows no influence on water transport process.     

Analysis of liquid water transport in cathode catalyst layer of PEM fuel cells

The performance of a polymer electrolyte membrane (PEM) fuel cell is significantly affected by liquid water generated at the cathode catalyst layer (CCL) potentially causing water flooding of cathode; while the ionic conductivity of PEM is directly proportional to its water content. Therefore, it is essential to maintain a delicate water balance, which requires a good understanding of the liquid water transport in the PEM fuel cells. In this study, a one-dimensional analytical solution of liquid water transport across the CCL is derived from the fundamental transport equations to investigate the water transport in the CCL of a PEM fuel cell. The effect of CCL wettability on liquid water transport and the effect of excessive liquid water, which is also known as “flooding”, on reactant transport and cell performance have also been investigated. It has been observed that the wetting characteristic of a CCL plays significant role on the liquid water transport and cell performance. Further, the liquid water saturation in a hydrophilic CCL can be significantly reduced by increasing the surface wettability or lowering the contact angle. Based on a dimensionless time constant analysis, it has been shown that the liquid water production from the phase change process is negligible compared to the production from the electrochemical process.     

Transient behavior of water generation in a proton exchange membrane fuel cell

The effect of water generation on the performance of proton exchange membrane fuel cell (PEMFC) was investigated by using a periodical linear sweep method. Three different kinds of I–V curves were obtained, which reflected different amount of water uptake in the fuel cell. The maximum water uptake that could avoid flooding in the fuel cell and the hysteresis of water diffusion were also discussed. Quantitative analysis of water uptake and water transport phenomena in this study were conducted both experimentally and theoretically. Results showed that the water uptake capacity for the fuel cell under no severe flooding was 27.837 mg cm⁻². The transient response of the internal resistance indicated that the high frequency resistance (HFR) lagged the current with a value of about 20 s. The effect of purging operation on the internal resistance of the fuel cell was also explored. Experimental data showed that the cell experienced a continuous 8-min purging process can maintain at a relatively steady and dry state.     

Evaluation of the net water transport through electrolytes in Proton Exchange Membrane Fuel Cell

Electro-osmotic drag and back diffusion are the primary water transport mechanisms in PEMFC (Proton Exchange Membrane Fuel Cell) electrolytes. These two phenomena occur competitively in the membrane, and ultimately determine the net water movement. The chemical compositions of reactants and product (i.e., H₂, O₂, and H₂O) in a porous catalyst layer vary with respect to the electro-chemical reactions and water transport through the membrane. The tendency of the chemical compositions was estimated by analyzing the net water transport coefficient (α), defined as the ratio of the reaction rate to the water transport rate. New criteria were suggested for predicting species mole fractions from the flow direction, and these were validated by CFD analysis. The hydrogen mole fraction had different tendencies to rise or fall based on the flow direction at α = 0.5, while the oxygen mole fraction extreme was located at α = −0.75. Finally, α was shown to influence the membrane conductivity and activation losses, which are the main factors that contribute to fuel cell performance.     

Laser-perforated anode gas diffusion layers for direct methanol fuel cells

Novel anode gas diffusion layers (AGDLs) with both hydrophobic and hydrophilic pathways are created to enhance transfer of both methanol and CO₂. Such AGDLs are created by perforating PTFE-treated AGDLs with laser, so that the original pores/pathways in the AGDL are hydrophobic and the laser perforations are hydrophilic, thus providing easy transport paths for both the liquid methanol solution and CO₂. One of the novel AGDLs has increased the cell performance by 32% over the non-perforated AGDL. Results of electrochemical impedance spectroscopy (EIS) show that the main reason for the performance enhancement is due to the reduction in mass transfer resistance. Additionally, there is a reduction in charge transfer resistances due to the enhanced methanol transfer to the catalyst layer. The results of linear sweep voltammetry (LSV) show that the perforations increase methanol crossover, thus if perforation density of the AGDL is too high, the cell performances are lower than that of the virgin AGDL.     

Effects of an MPL on water and thermal management in a PEMFC

In this study, the effects of adding a microporous layer (MPL) as well as the impact of its physical properties on polymer electrolyte fuel cell (PEMFC) performance with serpentine flow channels were investigated. In addition, numerical simulations were performed to reveal the effect of relative humidity and operating temperature. It is indicated that adding an extra between the gas diffusion layer (GDL) and catalyst layer (CL), a discontinuity in the liquid saturation shows up at their interface because of differences in the wetting properties of the layers. In addition, results show that a higher MPL porosity causes the liquid water saturation to decrease and the cell performance is improved. A larger MPL thickness reduces the cell performance. The effects of MPL on temperature distribution and thermal transport of the membrane prove that the MPL in addition to being a water management layer also improves the thermal management of the PEMFC.     

Experimental study on water transport coefficient in Proton Exchange Membrane Fuel Cell

Water transport within Proton Exchange Membrane Fuel Cell (PEMFC) is investigated by systematic measurements of the water transport coefficient, defined as the net water flux across the membrane divided by the water production. It is recorded for various operating conditions (current density, gas stoichiometry, air inlet relative humidity, temperature, pressure) in a fuel cell stack fed by dry hydrogen. The measurement of the water transport coefficient shows that a significant fraction of water is collected at the anode while water is produced or injected at the cathode. Moreover, in usual operating conditions, liquid water is present at the cell outlet not only in the cathode but also in the anode. Contrary to the electrical performances, ageing has no influence on the water transport coefficient, which allows the comparison between data collected at different periods of the fuel cell lifetime. From this comparison, it was found that the hydrogen flow rate, the amount of vapor injected at cathode inlet, and the temperature are the main parameters influencing the water transport coefficient. It is shown that air and hydrogen stoichiometry present significant effects on water transport but only through these parameters.     

Lattice Boltzmann simulations of water transport in gas diffusion layer of a polymer electrolyte membrane fuel cell

The effect of wettability on water transport dynamics in gas diffusion layer (GDL) is investigated by simulating water invasion in an initially gas-filled GDL using the multiphase free-energy lattice Boltzmann method (LBM). The results show that wettability plays a significant role on water saturation distribution in two-phase flow in the uniform wetting GDL. For highly hydrophobicity, the water transport falls in the regime of capillary fingering, while for neutral wettability, water transport exhibits the characteristic of stable displacement, although both processes are capillary force dominated flow with same capillary numbers. In addition, the introduction of hydrophilic paths in the GDL leads the water to flow through the hydrophilic pores preferentially. The resulting water saturation distributions show that the saturation in the GDL has little change after water breaks through the GDL, and further confirm that the selective introduction of hydrophilic passages in the GDL would facilitate the removal of liquid water more effectively, thus alleviating the flooding in catalyst layer (CL) and GDL. The LBM approach presented in this study provides an effective tool to investigate water transport phenomenon in the GDL at pore-scale level with wettability distribution taken into consideration.     

Water transport in polymer electrolyte membrane fuel cells

Polymer electrolyte membrane fuel cell (PEMFC) has been recognized as a promising zero-emission power source for portable, mobile and stationary applications. To simultaneously ensure high membrane proton conductivity and sufficient reactant delivery to reaction sites, water management has become one of the most important issues for PEMFC commercialization, and proper water management requires good understanding of water transport in different components of PEMFC. In this paper, previous researches related to water transport in PEMFC are comprehensively reviewed. The state and transport mechanism of water in different components are elaborated in detail. Based on the literature review, it is found that experimental techniques have been developed to predict distributions of water, gas species, temperature and other parameters in PEMFC. However, difficulties still remain for simultaneous measurements of multiple parameters, and the cell and system design modifications required by measurements need to be minimized. Previous modeling work on water transport in PEMFC involves developing rule-based and first-principle-based models, and first-principle-based models involve multi-scale methods from atomistic to full cell levels. Different models have been adopted for different purposes and they all together can provide a comprehensive view of water transport in PEMFC. With the development of computational power, application of lower length scale methods to higher length scales for more accurate and comprehensive results is feasible in the future. Researches related to cold start (startup from subzero temperatures) and high temperature PEMFC (HT-PEMFC) (operating at the temperatures higher than 100 °C) are also reviewed. Ice formation that hinders reactant delivery and damages cell materials is the major issue for PEMFC cold start, and enhancing water absorption by membrane electrolyte and external heating have been identified as the most effective ways to reduce ice formation and accelerate temperature increment. HT-PEMFC that can operate without liquid water formation and membrane hydration greatly simplifies water management strategy, and promising performance of HT-PEMFC has been demonstrated.